CN103881765A - Split circulating CO transformation process - Google Patents
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Abstract
The invention relates to a split circulating CO transformation process, comprising the following steps: separating liquid from a crude synthesis gas of saturated steam conveyed from a pulverized coal gasification unit and preheating to certain temperature, and then entering a detoxification slot to remove impurities and heavy metal; then dividing the liquid without impurities and heavy metal into two strands, wherein the first strand of the liquid is mixed with high-pressure steam and a first strand of variable mixed gas and supplied to a medium-pressure boiler to supply water; entering a 1# shift converter to carry out shift reaction, and dividing the obtained variable mixed gas into two strands after heat exchange; entering a 2# shift converter to carry out shift reaction after mixing the second strand of variable mixed gas with the second strand of fresh synthesis gas; entering the obtained divalent mixed gas into a 3# shift converter to further carry out shift reaction after heat exchange. The CO concentration of the shift converter is effectively reduced by splitting the crude synthesis gas and the variable mixed gas, the operation temperature of the shift converter is low, the operation environment of the catalyst is mild, the stable operation cycle of the device is prolonged, and the energy conservation and consumption reduction effects are good.
Description
Technical field
The present invention relates to a kind of CO conversion process, specifically refer to a kind of share split circulation CO conversion process.
Background technology
China's Coal Gasification Technology has obtained tremendous development in recent years, especially adopt the powdered coal pressuring gasified technology of waste heat boiler flow process, have ature of coal is required in low, synthetic gas, active principle is high, working cost is low and the feature such as environmental friendliness, adopted by domestic increasing large-scale coal chemical engineering equipment.In the crude synthesis gas that the powdered coal pressuring gasified technology of waste heat boiler flow process generates, CO butt volume content is conventionally up to more than 60%, and water vapor volume content is less than 20% simultaneously, and crude synthesis gas has the low and high distinguishing feature of CO content of vapour content.
The powdered coal pressuring gasified technology of waste heat boiler flow process all needs to configure CO shift conversion step while carrying out the devices such as supporting synthetic ammonia, hydrogen manufacturing, synthesizing methanol for gas making, regulate the hydrogen-carbon ratio in synthetic gas maybe as far as possible many CO to be transformed to hydrogen by conversion.Therefore, no matter be the high concentration CO converter technique difficult problem that the products such as production synthetic ammonia or methyl alcohol are all faced with strong heat release, so popularization and the development in recent years of the powdered coal pressuring gasified technology of waste heat boiler flow process, has also promoted the development and progress of China's high concentration CO converter technique greatly.
Transformationreation is the reaction with same mole of water vapor and CO, emits a large amount of reaction heat when generating carbonic acid gas and hydrogen.The crude synthesis gas generating for different Coal Gasification Technology, the chemical reaction process of shift conversion step is all identical, but shift process need design targetedly according to the feature of crude synthesis gas.Add for the fine coal that adopts waste heat boiler flow process the crude synthesis gas that the technology of calming the anger generates, in the time that shift conversion step carries out CO transformationreation, the Focal point and difficult point of shift process design is bed temperature how effectively to control CO transformationreation, extends the work-ing life of transformation catalyst and reduces transformationreation energy consumption.
Be matched at present the shift process of this gasification technology, more general employing the sulfur resistant conversion process of high water-gas ratio, before shift conversion step is all arranged on crude synthesis gas desulfurization.Adopt high water-gas ratio sulfur resistant conversion process, its process features is to become in advance stove overtemperature in order to prevent, in the pre-disposable interpolation of shift converter entrance is a large amount of, press superheated vapour, water/dry gas mol ratio in crude synthesis gas is reached more than 1.30, then transformationreation is carried out in segmentation, and final conversion gas outlet CO butt volume content is not generally higher than 0.4%.
Existing high water-gas ratio CO shift process is in order to suppress the overtemperature of transformationreation, in allocating in a large number, press superheated vapour before crude synthesis gas enters pre-shift converter, make its water/dry gas mol ratio reach 1.3～1.5, even but like this, due to the high and violent thermopositive reaction of CO concentration in crude synthesis gas, still often there is pre-shift converter overtemperatute in device in operational process.Once overtemperature must cause pre-change catalyzer activity sharply to fail, catalyst change is frequent, affects the long-period stable operation of changing device; Owing to need to allocating more middle pressure superheated vapour into, cause the high running cost of plant energy consumption large simultaneously.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of share split circulation CO conversion process for the present situation of prior art, to solve the series of technical such as the catalyst life that the easy overtemperature of existing high water-gas ratio CO conversion process shift converter caused is short, energy consumption is high.
The present invention solves the problems of the technologies described above adopted technical scheme: this share split circulation CO conversion process, is characterized in that comprising the steps:
Saturated 155 ℃～165 ℃ of crude synthesis gas temperature, the pressure 3.65Mpa(G of water vapor being sent here by coal gasification unit)～3.75Mpa(G), water/dry gas mol ratio 0.18～0.19, CO butt volume content 60%～70%, enter gas-liquid separator separates go out liquid laggard enter synthetic gas preheater be preheated to 215 ℃～225 ℃ of temperature, enter detoxification groove and remove impurity and the heavy metal in crude synthesis gas;
The fresh synthesis gas that goes out detoxification groove is divided into two strands, the first strand of fresh synthesis gas that wherein accounts for total amount 20%～30v% with utilize 535 ℃～540 ℃ of high-pressure steam ejector injection temperatures, pressure 9.0Mpa(G)～11.0Mpa(G) and high pressure steam produce first strand of 20%～25v% that power sucks and become gas mixture and mix, then enter gas liquid mixer and the medium pressure boiler filling into and feed water and enter 1# shift converter after mixing and carry out transformationreation; Control enters 245 ℃～255 ℃ of the mixture temperatures of 1# shift converter, CO butt volume content 40%～45%, water/dry gas mol ratio 1.3～1.5;
The conversion gas temperature that goes out 1# shift converter is 390～420 ℃, CO butt volume content 2%～4%, water/dry gas mol ratio 0.7～0.8; Going out one of 1# shift converter becomes gas mixture and enters in 1# and to press 250 ℃ of useless pot output temperature, the middle pressure saturation steam of pressure 4.0Mpa (G), after mixing with the middle pressure saturation steam of pressing useless pot to produce in the 2# of downstream, fill in a change gas mixture, now a change mixture temperature is down to 270 ℃～290 ℃, be divided into two strands, the first strand of one change gas mixture that wherein accounts for a change gas mixture total volumetric flow rate 20%～25v% aspirates the entrance that turns back to 1# shift converter by high-pressure steam ejector; Remaining is after second strand of one change gas mixture mixes with second strand of fresh synthesis gas, to enter 2# shift converter to carry out transformationreation; The temperature of controlling 2# shift converter entrance gas mixture is that 245～255 ℃, CO butt volume content 38%～45%, water/dry gas mol ratio are 0.75～0.85;
Go out two of 2# shift converter become mixture temperatures into 420～435 ℃, CO butt volume content 6%～8%, water/dry gas mol ratio be 0.35～0.45; Enter the middle pressure saturation steam of pressing 250 ℃ of useless pot output temperature, pressure 4.0Mpa (G) in 2#, two change mixture temperatures are down to 260～270 ℃ simultaneously, after the heat exchange of crude synthesis gas preheater, temperature is down to 220 ℃～230 ℃ again, enter 3# shift converter and proceed transformationreation, the three change mixture temperatures that go out 3# shift converter are 260 ℃～270 ℃, CO butt volume content is 1%～1.5%, water/dry gas mol ratio 0.25～0.35.Three become gas mixtures enters 130 ℃ of the temperature that the preheating of oiler feed interchanger sent here by battery limit (BL), the medium pressure boiler feedwater of pressure 5.0Mpa (G), and by medium pressure boiler feed-water preheating to 200 ℃, three become after mixture temperatures are down to 210 ℃～230 ℃ and send downstream.
Compared with prior art, the invention has the advantages that:
1, circulate by the lower concentration CO that utilizes vapo(u)r blasting to suck after conversion, effectively reduce the CO concentration that enters shift converter, reached shift converter service temperature and reduced, catalyzer running environment gentleness, catalyzer is elongated work-ing life, and converter unit is easily realized the object of long-period stable operation;
2, in whole transformationreation process, a water/dry gas mol ratio becoming in gas mixture that only has the fresh crude synthesis gas of 20%～30v% and partly loop back reaches 1.3～1.5, but the water-gas ratio of whole transformation system is lower all the time, reduce the consumption of middle pressure superheated vapour.
3, the self-produced steam of converter unit, all for the transformationreation of self, has saved sect heat-exchanger and energy recovery equipment, has simplified technical process, has saved facility investment.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the embodiment of the present invention.
Embodiment
Below in conjunction with accompanying drawing embodiment, comparative example, the present invention is further elaborated.
Embodiment
The CO conversion process of the present embodiment is to support the use the typical chemical fertilizer plant of producing 520,000 tons/year of urea of 300,000 tons/year of synthetic ammonia in Shell Coal Gasification gas making.
As shown in Figure 1, this share split circulation CO conversion process comprises the steps:
155 ℃～165 ℃ of the synthetic gas temperature of the saturated water vapor of being sent here by coal gasification unit, pressure 3.65Mpa(G)～3.75Mpa(G), water/dry gas mol ratio 0.18～0.19, CO butt volume content 60%～70%, the process of with pipeline, raw gas being delivered to converter unit from gasification unit due to calorific loss, a small amount of water vapour in synthetic gas generation phlegma that can be condensed, synthetic gas and lime set coexist and can cause corrosion and the vibrations of pipeline and equipment in tubing system, so synthetic gas needed lime set wherein to separate before entering pre-shift converter, therefore, this example is first sent into synthetic gas gas-liquid separator 1, isolated liquid is discharged from the bottom of gas-liquid separator 1.From gas-liquid separator 1 top, synthetic gas is out preheated to 215 ℃～225 ℃ of temperature through synthesizer preheater 9, enters detoxification groove 2 and removes impurity and the heavy metal in synthetic gas.The synthetic gas that goes out detoxification groove 2 is called fresh synthesis gas, and this gas is divided into two strands.Wherein first strand of fresh synthesis gas accounts for 20%～30% of volume total amount, with utilize 535 ℃～540 ℃ of high-pressure steam ejector 3 injection temperatures, pressure 9.0Mpa(G)～11.0Mpa(G) and high pressure steam produce power suck account for volume total amount 20%～25% one become gas mixture mix, then enter gas liquid mixer 4 and mix with the medium pressure boiler feedwater filling into, temperature and water-gas ratio are finely tuned.Control enters 245 ℃～255 ℃ of the mixture temperatures of 1# shift converter 5, CO butt volume content 40%～45%, and water/dry gas mol ratio 1.3～1.5, enters 1# shift converter 5 and carries out depth conversion reaction.
After the 5 depth conversion reactions of 1# shift converter, the conversion gas temperature that goes out 1# shift converter 5 is about 390～420 ℃, CO butt volume content 2%～4%, water/dry gas mol ratio 0.7～0.8.One becomes gas mixture enters in 1# and to press 250 ℃ of useless pot 6 output temperature, the middle pressure saturation steam of pressure 4.0Mpa (G), fill in a change gas mixture after mixing with the useless pot of pressure 8 middle pressure saturation steams that produce in the 2# of downstream, now a change mixture temperature is down to 270 ℃～290 ℃, be divided into two strands, wherein one change gas mixture that accounts for volume total amount 20%～25% turns back to the entrance of 1# shift converter 5 by high-pressure steam ejector 3 suctions; One accounts for one of volume total amount 75%～80% and becomes gas mixture in addition, infiltrates into 2# shift converter 7 and carries out transformationreation with second strand of fresh synthesis gas that accounts for fresh synthesis gas total amount 70%～80%.Wherein the temperature of 2# shift converter 7 entrance gas mixtures is 245～255 ℃, CO butt volume content 38%～45%, and water/dry gas mol ratio is 0.75～0.85.
After the 7 depth conversion reactions of 2# shift converter, the two change mixture temperatures that go out 2# shift converter 7 are 420～435 ℃, CO butt volume content 6%～8%, and water/dry gas mol ratio is 0.35～0.45.Enter in 2# and to press 250 ℃ of useless pot 8 output temperature, the middle pressure saturation steam of pressure 4.0Mpa (G), two change mixture temperatures are down to 260～270 ℃ simultaneously, again after 9 heat exchange of crude synthesis gas preheater temperature be down to～230 ℃, enter 3# shift converter 10 and proceed transformationreation, the three change mixture temperatures that go out 3# shift converter 10 are 260 ℃～270 ℃, and CO butt volume content is 1%～1.5%, water/dry gas mol ratio 0.25～0.35.Three become gas mixtures enters 130 ℃ of the temperature that 11 preheatings of oiler feed interchanger are sent here by battery limit (BL), the medium pressure boiler feedwater of pressure 5.0Mpa (G), and by medium pressure boiler feed-water preheating to 200 ℃, three become after mixture temperatures are down to 210 ℃～230 ℃ and send downstream.
Comparative example
China Petrochemical Industry's Anqing oil changes gas project and has adopted the powdered coal pressuring gasified technology gas making of shell, for the production of 520,000 tons/year of urea of 300,000 tons/year of synthetic ammonia, adopted high water-gas ratio CO shift process, gasification unit send effective gas (H2+CO) of converter unit to be approximately 85000Nm3/h.The significant parameter of itself and above-described embodiment is contrasted, the results are shown in Table 1
Shown in.
Table 1
* change the high water-gas ratio CO conversion process in 520,000 tons/year of urine devices of 300,000 tons/year of synthetic ammonia of gas project for supporting at Anqing oil.
* is the mixture of described first strand of fresh synthesis gas and described first strand of one change gas mixture.
Can find out by table 1, share split circulation CO conversion new technology provided by the present invention, effectively reduces the CO concentration that enters shift converter, all plays good result to extending in the control of shift converter temperature, the optimization of catalyzer running environment and work-ing life.The steam consumption of whole transformation system has also been realized significantly and having been reduced simultaneously, significant to the energy-conservation of converter unit and reduction enterprise operation expense.
Claims (1)
1. a share split circulation CO conversion process, is characterized in that comprising the steps:
Saturated 155 ℃～165 ℃ of crude synthesis gas temperature, the pressure 3.65Mpa(G of water vapor being sent here by coal gasification unit)～3.75Mpa(G), water/dry gas mol ratio 0.18～0.19, CO butt volume content 60%～70%, enter gas-liquid separator (1) and isolate and enter synthetic gas preheater (9) after liquid and be preheated to 215 ℃～225 ℃ of temperature, enter detoxification groove (2) and remove impurity and the heavy metal in crude synthesis gas;
The fresh synthesis gas that goes out detoxification groove (2) is divided into two strands, the first strand of fresh synthesis gas that wherein accounts for total amount 20%～30% with utilize 535 ℃～540 ℃ of high-pressure steam ejector (3) injection temperatures, pressure 9.0Mpa(G)～11.0Mpa(G) and 20%～25% first strand of producing that power sucks of high pressure steam become gas mixture and mix, then enter gas liquid mixer (4) and the medium pressure boiler filling into and feed water and enter 1# shift converter (5) after mixing and carry out transformationreation; Control enters 245 ℃～255 ℃ of the mixture temperatures of 1# shift converter (5), CO butt volume content 40%～45%, water/dry gas mol ratio 1.3～1.5;
The conversion gas temperature that goes out 1# shift converter (5) is 390～420 ℃, CO butt volume content 2%～4%, water/dry gas mol ratio 0.7～0.8; Going out one of 1# shift converter (5) becomes gas mixture and enters in 1# and to press 250 ℃ of useless pot (6) output temperature, the middle pressure saturation steam of pressure 4.0Mpa (G), after mixing with the middle pressure saturation steam of pressing useless pot (8) to produce in the 2# of downstream, fill in a change gas mixture, now a change mixture temperature is down to 270 ℃～290 ℃, be divided into two strands, the first strand of one change gas mixture that wherein accounts for a change gas mixture total volumetric flow rate 20%～25% turns back to the entrance of 1# shift converter (5) by high-pressure steam ejector (3) suction; Remaining is after second strand of one change gas mixture mixes with second strand of fresh synthesis gas, to enter 2# shift converter (7) to carry out transformationreation; The temperature of controlling 2# shift converter (7) entrance gas mixture is that 245～255 ℃, CO butt volume content 38%～45%, water/dry gas mol ratio are 0.75～0.85;
Go out two of 2# shift converter (7) become mixture temperatures into 420～435 ℃, CO butt volume content 6%～8%, water/dry gas mol ratio be 0.35～0.45; Enter the middle pressure saturation steam of pressing useless 250 ℃ of () 8 output temperature of pot, pressure 4.0Mpa (G) in 2#, two change mixture temperatures are down to 260～270 ℃ simultaneously, after crude synthesis gas preheater (9) heat exchange, temperature is down to 220 ℃～230 ℃ again, enter 3# shift converter (10) and proceed transformationreation, the three change mixture temperatures that go out 3# shift converter (10) are 260 ℃～270 ℃, CO butt volume content is 1%～1.5%, water/dry gas mol ratio 0.25～0.35; Three become gas mixtures enters 130 ℃ of the temperature that oiler feed interchanger (11) preheating sent here by battery limit (BL), the medium pressure boiler feedwater of pressure 5.0Mpa (G), by medium pressure boiler feed-water preheating to 200 ℃, after being down to 210 ℃～230 ℃, three change mixture temperatures send downstream.
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| CN104152187A (en) * | 2014-08-06 | 2014-11-19 | 中石化宁波工程有限公司 | CO conversion process capable of prolonging service life of catalysts |
| CN104340958A (en) * | 2013-07-30 | 2015-02-11 | 航天长征化学工程股份有限公司 | high-CO raw gas conversion process obtained by pressure gasification of pulverized coal |
| CN105905869A (en) * | 2016-04-14 | 2016-08-31 | 中石化南京工程有限公司 | Coal-to-hydrogen CO conversion poly-generation method and device |
| CN110921621A (en) * | 2019-10-24 | 2020-03-27 | 中石化宁波工程有限公司 | Low-steam-ratio poly-generation isothermal transformation process and isothermal transformation furnace matched with pulverized coal gasification |
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